Four novel In3+ and Cd2+ based 1D coordination compounds constructed by double betaine ligands were synthesized and characterized structurally and optically. They assemble into 3D supra‐molecular architectures via different stacking or entanglement of 1D zigzag shaped chains, in which C–H···Cl and C–H···O hydrogen bonding interactions play a dramatic impact. Compound 1 displays a 1D + 1D → 3D four‐connect lvt net with 42·84 topology. Compound 2 assembles into a 3D architecture by inclined stacking of the adjacent zigzag chains. Compound 3 displays a 2D + 2D → 3D inclined polycatenation based on the resulting 2D (6, 3) layers that constructed by 1D chains. Compound 4 displays a 3D supra‐molecular architecture based on 1D chains, which were connected via the hydrogen bonding. Meanwhile, four compounds emit in the range of visible region owing to the intra‐ligand π*→π and/or π*→n electron transition induced florescence.